لایب سان

1 INORGANIC POLYMERS AND CLASSIFICATION SCHEMES 1 1.1 Introduction 1 1.1.1 What Is an Inorganic Polymer? 2 1.2 Classifications by Connectivities 3 1.2.1 Connectivities of 1 3 1.2.2 Connectivities of 2 5 1.2.3 Connectivities of 3 6 1.2.4 Mixed Connectivities of 2 and 3 8 1.2.5 Connectivities of 4 9 1.2.6 Mixed Connectivities of 3 and 4 9 1.2.7 Connectivities of 6 9 1.2.8 Mixed Connectivities of 4 and 6 11 1.2.9 Connectivities of 8 12 1.3 Classifications by Dimensionality 12 1.3.1 1-D Polymeric Structures 12 1.3.2 2-D Polymeric Structures 13 1.3.3 3-D Polymeric Structures 15 1.4 The Metal/Backbone Classification of Metal-Containing Polymers 16 1.4.1 Type I Metal-Backbone Polymers 17 1.4.2 Type II Metal-Enmeshed Polymers 18 vii viii CONTENTS 1.4.3 Type III Anchored Metal Polymers 19 1.5 Linear Inorganic Polymers — The Thrust of this Book 20 1.5.1 Metal-Containing Polymers 20 1.5.2 Main Group Inorganic Polymers 25 References 31 Exercises 32 2 INORGANIC POLYMER SYNTHESES 35 2.1 Step-Growth Syntheses 35 2.1.1 Step Condensation Synthesis Generalities 36 2.1.2 Step Condensation Syntheses of Metal-Containing Polymers 40 2.1.3 Main Group Step Condensation Polymer Syntheses 52 2.1.4 Step Addition Syntheses 57 2.2 Chain Polymerizations 58 2.2.1 Radical Polymerizations 60 2.2.2 Cationic Polymerizations 65 2.2.3 Anionic Polymerizations 68 2.3 Ring-Opening Polymerizations 69 2.3.1 Metal-Coordination ROP 70 2.3.2 Organometallic ROP 70 2.3.3 Main Group ROP 73 2.4 Reductive Coupling and Other Redox Polymerization Reactions 78 2.4.1 Reductive Coupling 78 2.4.2 Oxidative Addition Polymerizations 80 2.5 Condensation (Desolvation) Oligomerizations/Polymerizations 81 2.5.1 Cationic Aggregations 82 2.5.2 Anionic Aggregations 82 2.5.3 Desolvation at Elevated Temperature 83 2.5.4 Solvolysis-Desolvation Reactions 83 2.6 Miscellaneous Synthesis Comments 84 2.6.1 Solubility 84 2.6.2 Telechelic Polymers 87 2.6.3 Catalyzed Dehydrogenation Reactions 87 References 87 Exercises 91 3 INORGANIC POLYMER CHARACTERIZATION 93 3.1 Average Molecular Masses and Degrees of Polymerization 94 CONTENTS ix 3.2 Methods of Characterizing Average Molecular Masses 99 3.2.1 Gel Permeation Chromatography 99 3.2.2 Viscosity 103 3.2.3 Universal Calibration 110 3.2.4 Light Scattering for Absolute Molecular Mass and Size Measurements 114 3.2.5 Colligative Properties (Vapor Pressure Lowering, Boiling Point Elevation, Melting Point Lowering, and Osmotic Pressure) 116 3.2.6 End-Group Analyses 119 3.2.7 Mass Spectroscopy 124 3.2.8 Ultracentrifugation 124 3.3 Determinations of Thermal Parameters 126 3.3.1 Glass Transition Temperature Measurements 127 3.3.2 Other Thermal Parameters 132 3.4 Spectroscopic Characterizations Specific to Inorganic Polymers 133 3.4.1 Nuclear Magnetic Resonance Spectroscopy 133 3.4.2 Electron Paramagnetic Resonance Spectroscopy 136 3.4.3 Electronic Spectroscopies 142 3.4.4 Vibrational Spectroscopies 152 3.4.5 Mossbauer Spectroscopy 158 ¨ 3.4.6 Other Spectroscopic Methods 165 3.5 Viscoelasticity Measurements 167 3.6 Crystallization Characterization 170 3.6.1 Birefringent Microscopy 171 3.6.2 Wide-Angle X-Ray Scattering 171 3.6.3 Small-Angle X-Ray Scattering 172 3.6.4 Small-Angle Polarized Light Scattering 172 3.6.5 Electron Scattering 172 3.6.6 Neutron Scattering 173 3.7 Concluding Statement 173 References 173 Exercises 177 4 PRACTICAL INORGANIC POLYMER CHEMISTRY 179 4.1 Inorganic Polymer Elastomers 179 4.1.1 Polysiloxane Elastomers 180 4.1.2 Polyphosphazene Elastomers 182 4.1.3 Other Inorganic Elastomers 186 x CONTENTS 4.2 Interface Coupling Reactions 186 4.2.1 Silicon Coupling Agents 186 4.2.2 Metal Coupling Agents 188 4.3 Inorganic Dental Polymers and Adhesives 193 4.4 Inorganic Medical Polymers 194 4.4.1 Polysiloxanes as Biopolymers 194 4.4.2 Polyphosphazenes as Biopolymers 197 4.4.3 Metal-Containing Polymers for Medical Purposes 198 4.5 Inorganic High-Temperature Fluids and Lubricants 198 4.6 Inorganic Polymers as Lithographic Resists 202 4.7 Inorganic Polymers as Preceramics 207 4.7.1 Silicon Carbide from Polycarbosilanes 207 4.7.2 Silicon Nitride Preceramic Polymers 209 4.7.3 Other Preceramic Polymers 210 4.8 Inorganic Polymer Conductivity 212 4.8.1 Main Group Inorganic Polymers 212 4.8.2 Metal-Containing Polymers 214 4.9 Nonlinear Optics Metal-Containing Polymers 217 4.10 Luminescent Inorganic Polymers 218 4.10.1 Ruthenium Polymers for Solar Energy Conversion 218 4.10.2 Other Luminescent Metal Polymers 221 4.10.3 Silicon Luminescent Materials 221 4.11 Magnetic Metal-Coordination Polymers 222 4.12 Inorganic Polymers as Catalysts 225 4.13 Miscellaneous Uses 226 References 226 Exercises 232 Epilogue 235 Index 237

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